JPS6028904A - Antifouling agent for fishing net - Google Patents

Abstract

PURPOSE:To provide an antifouling agent having high stability, effective to control the adhesion of marine life to a fishing net, and containing an N-fluorodichloromethylthio derivative and N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)-phthalimide. CONSTITUTION:The objective agent contains the N-(fluorodichloromethylthio)- phthalimide of formula I and/or the N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)-sulfamide of formula II as active components. The active components are dispersed or dissolved homogeneously in a spreader and a solvent, and if necessary, a coloring dye is added to the dispersion, etc. to obtain the objective antifouling agent. The amount of the active components in the agent is preferably 3-50%. The spreader is e.g. a resin such as rosin, and the solvent is e.g. mineral spirit, etc. The antifouling agent is applied to the fishing net preferably by immersing the net in the agent, and drying the agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel fishing net that is effective and safe and does not contain any metal components, and is used to control marine pests that adhere to fishing nets such as aquaculture nets and fixed nets. Regarding antifouling agents.

More specifically, the present invention uses formula (1) as an active ingredient.
N-(fluorodichloromethylthio)-
Tutarimide and/or represented by formula (2),
The present invention relates to an antifouling agent for fishing nets containing N,N-dimethyl-d-phenyl-〇=-'(fluorodichloromethylthio)-sulfamide.

Fishing nets such as aquaculture nets and fixed nets that are left in seawater for long periods of time are used for fishing nets that are left in seawater for long periods of time.
Marine flora and fauna such as water beetles, sea lettuce, and green laver attach to the surface, causing many harmful effects.

For example, if marine organisms attach to aquaculture nets, the nets become clogged and the flow of seawater is obstructed, which inhibits the growth of fish, induces fish diseases, and in extreme cases can even lead to death. The impact is enormous.

Furthermore, when marine organisms adhere to fixed nets, ocean current resistance increases, leading to poor net quality, which not only dramatically reduces the amount of fish caught, but also significantly shortens the lifespan of the nets.

To prevent such marine organisms from adhering to fishing nets, K.
Fishing net antifouling agents have been considered and used for a long time. This fishing net antifouling agent has the following properties: it continues to have an antifouling effect for a long period of time, it has little fish irritant, it is safe because it does not cause rashes on the human body during fishing work, and it does not accumulate. It is necessary to not take responsibility for the cause of pollution, and to do all sorts of things.

However, at present, none of the existing antifouling agents for fishing nets completely satisfies these conditions.

Conventionally, as typical antifouling agents for fishing nets, various organometallic compounds, such as organocopper compounds such as copper naphthenate and copper oleate, and organotin compounds such as tributyltin oxide and triphenyltin chloride, have been applied to vinyl resins and acrylics. Books that have been dissolved and dispersed in resin have been used, but these have the disadvantage that their antifouling effects do not last for a long time and that marine organisms can adhere to them within a short period of time. If a large amount of toxic ingredients are added, safety for humans and fish will be greatly compromised, and there are concerns that the metal components dissolved from the antifouling agent will accumulate in the environment over a long period of time, causing negative effects. This is not a desirable product because of the drawbacks in terms of safety and health as well as environmental protection, and in recent years, fishing net antifouling agents containing organic tin copolymers as an active ingredient have come into wide use.

A fishing net antifouling agent containing this organic tin copolymer as an active ingredient is a type of fishing net antifouling agent in which an organic tin compound is chemically bonded to a resin skeleton, and it constantly releases a certain amount of toxic components into seawater through hydrolysis. Because it is released into the air, it maintains a constant antifouling effect for a long period of time, and it is also characterized by greatly improved safety for humans and fish.

However, since this organotin polymer contains a metal component called tin as an active ingredient, questions have been raised regarding its safety, health, and environmental protection, and it cannot be said that its safety has been completely proven. This is the current situation.

Under these circumstances, research is being conducted extensively on so-called non-metallic antifouling agents for fishing nets that do not contain any gold particles as active ingredients, that is, use nonmetallic compounds. An ideal antifouling agent that has both antifouling properties has not yet been developed.
Organic chlorine compounds such as H and C cannot be used because they accumulate in the environment, and organic arsenic compounds such as phenarsazine chloride cannot be used because they are irritating to the human body. Thiuram disulfide compounds and sufushiimide compounds have almost no antifouling properties and cannot be used, and there is a strong need for the development of non-metallic antifouling agents for fishing nets that have both antifouling properties and safety. In view of the current situation, the present inventors investigated an antifouling agent for fishing nets containing a nonmetallic compound as an active ingredient that has an antifouling effect and safety, and found that N-fluorodichloromethylthio derivatives The present invention was achieved by discovering the following effects.

That is, the present invention provides N-(fluorodichloromethylthio)-phthalimide and/l or N,N-dimethyl-
N'-phenyl-#-(fluorodichloromethylthio)
-An antifouling agent for fishing nets containing sultubamide as an active ingredient.

N-(fluorodichloromethylthio)-phthalimide and N,N-dimethyl-gophenyl-N'-, -(fluorodichloromethylthio)- which are the active ingredients of the present invention
The safety of sulfamide for the human body is very high, for example, the oral toxicity value for rats (LDs o Hat,
2900 rprg/kq for N-(fluorodichloromethylthio)-phthalimide.

4760■ for N,N-dimethyl-N'-phenyl-N'-(fluoro-dichloromethylthio)-sulfamide
/9, tributyltin oxide (T
, B, T, O)'s actual Kto~20 compared to 234 hits/yu
Not only is it twice as safe, but once dissolved in the sea, it hydrolyzes and loses toxicity in a relatively short period of time. Since it does not contain any gold FA atoms, it has many safety characteristics such as not causing environmental pollution due to the accumulation of metal toxic substances produced by decomposition.

Even more surprisingly, the present inventors found that these two active ingredients
It was discovered that it has an effective antifouling effect against a wide range of marine organisms such as water bugs, sea lettuce, and blue seaweed, and in particular, it has an outstanding control effect against marine animals such as Fujibbo, Serpura, and Sarcoptera. It was confirmed that it has ideal properties as an antifouling agent for fishing nets.

N-(fluorodichloromethylthio)-phthalimide and N,N-dimethyl-N'-phenyl-N of the invention
'-(Fluorodichloromethylthio)-sulfamide may be used alone or in combination, and in addition to other metal-containing antifouling agents, the amount of metal-containing antifouling agents used It is also possible to reduce this and improve safety.

Metal-containing antifouling agents used in combination for this purpose include cuprous oxide, copper rhodanide, copper stearate, copper naphthenate,
Inorganic and organic copper compounds such as copper oleate and copper acetate, tributyltin oxide, tributyltin chloride,
Examples include organic tin compounds such as triphenyltin hydroxide and triphenyltin dimethyldithiocarbamate, and metal salts of dithiocarnocimate such as zinc ethylenebisdithiocarbamate and manganese ethylenebiscarbamate.

The fishing net antifouling agent of the present invention has an active ingredient of N-(fluorodichloromethylthio)-7talimide and/or N-
, N-dimethyl-N'-phenyl-1=-(fluorodichloromethylthio)-sulfamide is dispersed under uniform pressure in a spreading agent and a solvent, and dissolved in natural or processed resins such as Elac, ester gum, or alkyd resins and acrylic resins. -Synthetic resins such as vinyl resins and chlorinated rubber resins, one or more of which are selected and used.

Examples of solvents include hydrocarbons such as mineral spirit, solvent naphtha, toluene, and xylene; ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; Optionally, one type or 2 g or more of a conventional organic solvent, such as an alcoholic solvent such as beer alcohol, may be used.

Fishing nets that can be treated with the antifouling agent for fishing nets of the present invention are made of any material, including natural fibers such as linen, silk, and wool, polyvinyl chloride, polyvinyl alcohol, and polyvinylidene chloride.・Nylon・Polyfluorinated ethylene・
This applies to all types of fishing nets, including synthetic fibers such as polyamide, polyethylene, polypropylene, polystyrene, and polyacrylonitrile.

When applying the antifouling treatment to the various fishing nets mentioned above using the fishing net antifouling agent of the present invention, the fishing net antifouling agent of the present invention is charged into a tank with an appropriate amount, and the fishing net is dipped in the tank and then dried. It is most suitable to apply by so-called dip coating.

In this way, by applying antifouling treatment to fishing nets of various species using the fishing net antifouling agent of the present invention,
It can effectively prevent the adhesion of a wide range of marine organisms such as the sea bream, water bug, sea lettuce, and green laver, as well as maintain safety during trenching work and protect the environment, so it can widely contribute to the development of the fisheries industry. It is.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, parts and parts in the examples are parts by weight and weight%, respectively.
shows.

(Examples 1 to 5) Based on the formulations shown in Table 1, each raw material was charged into a steel receiver, uniformly dispersed and dissolved using Desilver, and Examples 1 to 5
An antifouling agent for fishing nets was obtained.

(Comparative Example 1.2) Based on the formulation shown in Table 1, each raw material containing a known non-metallic antifouling agent as the main component was charged into a steel resin, uniformly dispersed and dissolved using a DeSilver, and compared. Antifouling agents for fishing nets of Examples 1 and 2 were obtained.

The antifouling agents for fishing nets of Examples 1 to 5 and Comparative Examples 1 and 2 were applied by dip coating on polyethylene aquaculture fishing nets (1 m x tfn), and then air-dried. The antifouling effects were compared using the evaluation criteria shown below.

The results are shown in Table 2.

Evaluation Criteria Table 2 Immersion test results As explained above in detail, the antifouling agent for fishing nets of the present invention does not contain any metal components and is extremely superior in terms of safety and environmental conservation. Since it can completely prevent the attachment of various marine organisms, it is clear that it will greatly contribute to the development of aquaculture and commercial fishing.

Patent applicant: NOF Corporation

Claims (1)

[Claims] N-(fluorodichloromethylthio)-7talimide and/or N,N-dimethyl-N'-phenyl-y
An antifouling agent for fishing nets containing -(fluorodichloromethylthio)-sulfamide as an active ingredient.